A Cu/Pd-catalyzed borylative coupling of allenes with allyl carbonates is reported. Synergistic Cu/Pd catalysis enables a divergent selectivity compared to Cu catalysis and allows for the regio-, diastereo-, and enantioselective formation of synthetically versatile chiral borylated 1,5-dienes featuring two adjacent tertiary stereocenters. DFT calculations support a closed inner-sphere S_E2′ transmetalation between the catalytic allyl copper and allyl palladium intermediates and point at the reductive elimination of the resulting bis(allyl)Pd intermediate as the regio- and diastereo-determining step.

中文翻译：

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通过协同催化改变硼化烯丙基-烯丙基交叉偶联的选择性


报道了铜/钯催化的丙二烯与碳酸烯丙酯的硼化偶联。与 Cu 催化相比，协同 Cu/Pd 催化可实现不同的选择性，并允许区域选择性、非对映选择性和对映选择性形成具有两个相邻三级立构中心的合成多功能手性硼酸化 1,5-二烯。 DFT 计算支持催化烯丙基铜和烯丙基钯中间体之间的封闭内球 S _E 2' 金属交换，并指出所得双（烯丙基）Pd 中间体作为区域和非对映体的还原消除确定步骤。